Water-insoluble monoazo dyestuffs

ABSTRACT

The invention comprises water-insoluble azo dyes of the general formula &lt;FORM:1024485/C4-C5/1&gt; where R is a nitro group-free residue of the benzene series, X is an acylamino radical, Y is hydrogen or halogen atom or a C1-C4 alkyl or C1-C4 alkoxy radical, R2 is a straight chain or branched unsubstituted or substituted C1-C4 alkyl radical or has the same meaning as R1, R1 denotes a grouping &lt;FORM:1024485/C4-C5/2&gt; where Z stands for a C2- 4 alkylene radical which may be substituted and R3 is a substituted or unsubstituted C1-C4 alkyl radical said dyes being free of sulphonic and carboxylic acid groups.  The dyes may also be prepared by reacting an appropriate dye containing a hydroxy group with a chloroformic acid alkyl ester to form the carbonate group.  The dyes are prepared by coupling an appropriate benzene series diazo component with an appropriate amine.  In an example, 4-cyano-aniline is diazotized and coupled with 1-N,N-di-[b (methoxycarbonyloxy) - ethyl] - amino - 3 - methoxyacetylamino - benzene to obtain an orange dye. Additional products are specified and a dyeing process described. The dyes are suitable for dyeing and printing textiles of polyethylene terephthalates, condensation products of terephthalic acid and 1,4-bis-hydroxy methyl - cyclohexane and cellulose acetates.

United States Patent 3,268,507 WATER-INSOLUBLE MONOAZO DYESTUFFS Winfried Krncltenberg, Leverkusen, Germany, assignor to Farbenfahriken Bayer Aktiengesellschaft, Leverlrusen, Germany, a corporation of Germany No Drawing. Filed Aug. 1, 1963, Ser. No. 299,692 Claims priority, application Germany, Aug. 10, 1962,

F 37,563; Mar. 28, 1963, F 39,347 14 Claims. (Cl. 260-407) The invention concerns new water-insoluble azo dyestuffs; more particularly it concerns new .2120 dyestuffs of the formula In this formula R stands for a residue of the benzene series, X stands for hydrogen, a lower alkyl, lower allroxy, halogen or acylamino group; Y means hydrogen, halogen, a lower alkyl or lower alkoxy group; R stands for a substituted or unsubstituted lower alkyl group, such as -CH C H C H (normal and iso), --C H (normal and iso), --C H4CN, B-carbo lower alkoxy ethyl or for a radical R R denotes a grouping wherein Z stands for .a lower alkyl group having 2-4 carbon atoms and R means a substituted or unsubstituted lower alkyl radical, such as the dyestulfs of Formula I shall be free of sulfonic acid and carboxylic acid groups.

The present invention includes the following compounds:

wherein K is a member selected from the class consisting of cyano, bromo, chloro, nitro, lower alkyl, lower alkoxy, canbo lower alkoxy, trifluormethyl, phenyl, lower al-kyl sulionyl, phenyl sul fonyl, carbonamide and lower alkylsubstituted carbonamide; L is a member selected from the class consisting of hydrogen, cyano and nitro; M is a member selected from the group consisting of chloro and bromo, n being an integer of 0-3 when M is chloro, and O-l when M is :bromo; X is a member selected from the class consisting of OH CONH, C H CO-NH--, CH OCH CO-NH, CH OOCNH-, NCOH CONH, ClCI-I CO-NH-, OHCH CONH, CH SO NH, C H SO NH, NH CONH, and C H CONH; Y is a member selected from the class consisting of hydrogen and lower alk-oxy; R is ZO(|3|ORs wherein Z is lower alkylene having 24 carbon atoms and R is a member selected from the group consisting of lower alkyl and cyano lower alkyl; R is a member selected from the group consisting of lower alkyl, cyano lower alkyl and -ZO( ORz 3,2685%? Patented August 23, 1966 Of additional interest are those compounds having the formula:

E o II w =N-C N 0112c n20 00113):

wherein D is a member selected from the class consisting of hydrogen, cyano, chloro and bromo; E is a member selected [from the class consisting of hydrogen, chloro, and bromo; A is a member selected from the group consisting of hydrogen, methyl, and methoxy; and B stands for a member selected from the class consisting of hydrogen and methoXy; and R is lower alkyl.

The novel Water-insoluble azo dyestuiis are obtained by coupling a diazo component of the benzene series, in para position to the group of a compound having the general formula wherein X, Y, R and R have the above significance, and the starting materials free of sulfonic acid and carboxylic acid groups.

The coupling of the starting components proceeds in the usual manner, preferably in acid aqueous solution or suspension. As diazo components of the benzene series there may be employed with especial advantage those which contain one or more cyano groups. Suitable diazo components are, inter alia:

2-eyano-6-bromo-4-nitroani-line,

2-cyano-5-chloro-4-nitroaniline, 2,4dicyano-6-chloroaniline, 2-methoXy-4-nitroanaline, Z-amino-S-nitro benzoic-acid methyl ester, 3-nitro-4-aminobenzoic acid butylester, 4-aminobenzoic acid methyl ester, 4-amino-benzoic acid alkyl amides,

such as -methyl or -dimethyl amide.

As coupling components the following amines can be used, for example:

l N-fl-cyanoethyl N (ethoxycarbonyloxy)ethylaminobenzene of the formula oirnoN l-N- (fi-canbomethoxyethyl) N- (fl-methoxycarbonyloxyethyl amino-3 methylbenzene,

1-N,N-di- (fl-methoxycanbonyloxyethyl amino-3- rnethylb enzene,

N,N-di-fl- (methoxycarb onyloxy) -ethylaminobenzene,

1 N,N-di- [B- (methoxy-car-b onyloxy) ethyl] amino- 3-acetylaminobenzene,

N(OHzCHzOCOCHa)z NH 0 COI-Ia l-N- p- (methoXy-carbonyloxy ethyl] N-fl-cyanoethyl- 3-acetylaminobenzene,

1-N- [fl- (methoxycarbonyloxy) -et-hyl] N-fi-carbomethoXyethyl-3 acetylaminobenzene,

1-N,N-di- [B-(methoxy-canbonyloxy) ethyl] 3-acetylamino-6-methoxy-benzene,

1-N,N-di- (methoXy-carb onyloxy) ethyl] 3-ureido- 6-ethoxy1benzene,

1 N,N-di- ,3-( me thoXy-carb onyloxy) ethyl] 3-acetylamino-6-methylibenzol,

1-N,N-di- [gB- (methoxycanbonyloxy) -ethyl] 3 carbometh oXy aminobenzene,

l-N- [ti-(methoxycarbonyloxy) ethyl] N-ethy1-3- acetylamino benzene,

l-N- p (isopropyloxycarbonyloxy) ethyl] N-ethyl-3- canbomethoxyaminob enzene,

1-N- [,8- (methoXy-carbonyloxy) ethyl] N-methyl-3- benzoylaminobenzene,

1-N, N-di- B-(ethoxy-carbonyloxy) ethyl] 3-rnethoxyacetylaminobenzene,

1N- [B-(methoxy-carbonyloxy) ethyl] N-propyl-3- oxyacetylaminobenzene,

l-N-ethyl-N- Bp dimethoxycarbonyloxy) propyl] -3- acetylamino benzene.

From the above list of the coupling components it will be understood that those dyestuffs are likewise within the scope of the invention which carry on the 2 to 4 carbon atoms-containing lower alkylene radical, i.e., Z, other substituents than the grouping II OCOR3 for instance a second O(||1OR3 group. The other alkyl residues in the novel dyestuffs, eLg. the radicals R and R, can, of course, likewise be further substituted and may be present as, e.g., halogenoalky-, such as chloroethyl groups, cyanoalkyl-, such as cyanoethyl groups, or carbo lower alkoxy substituted alkyl groups, such as carbomethoxyor canboethoxyethyl radicals. The list of coupling components further shows that a great variety of acylamino groups may be present in the azo component, among which lower aliphatic acyl groups and the non-ionic substitution products thereof, such as chloroor alkoxyor cyano-acetylamino groups, furthermore lower al-kylsulfonylor arylsulfonylamino groups, such as methylsulfonyl-, ethylsulfonyl-, propylsulfonyland phenylsulfonylamino groups and the nonionically substituted derivatives thereof, the urea grouping and the N-substitution products thereof, and carbo lower alkoxy amino (urethane) groups are of particular importance.

The coupling components ('11) may be obtained by reacting, -for instance, anilinewhich may bear the substituents X and Y, e.g., a mono acylated m-phenylenediamine, with ethyleneoxide according to common methods at about C. whereupon the N,N-di-(hydroxyethyD-derivative is obtained, and subsequently reacting the product in pyridine with a chloro formic acid al-kyl-ester to yield the corresponding carbonate.

The novel azo dyestuffs may also be prepared according to a variation of the aforementioned process by forming the carbonate gr-oup(s) in the final step of the process; for this purpose diazo components of the indicated type are coupled with such coupling components of the Formula II which instead of contain the corresponding ZOH group(s), and the hydroxyethylamino group-containing dyestuffs are finally reacted with, for instance, a chloro formic acid alkyl ester to form a carbonate group-containing dyestutf (I); the processes may be further varied in that an acylamino group X may be saponified and in a final step again acylated by means of other acylating agents.

The dyestuffs obtainable according to the invention are excellently suitable for dyeing and printing of hydrophobic materials, such as textiles or fibres of aromatic polyesters, e.g., polyethylene-terephthalates or condensation products of terephthalic acid and 1,4-(bis-hydroxymethyl)cyclohexane. On these materials dyeings and printings of very good fastness properties, especially very good fa-stness to light, wet processing, such as to washing, and to sublimation and to thermofixing are obtained. The novel dyestuffs are further distinguished by very good drawing power onto the said polyester materials.

The dyestuffs are also suitable for dyeing and printing cellulose acetate (2 /2 acetate) and triacetyl cellulose, and fibre materials of synthetic superpolyamides and polyacrylonitrile. The dyestufis are further distinguished by good crystallizability.

The following examples are given for the purpose of illustrating the invention without, however, limiting it thereto.

Example 1 16.3 parts by weight of 2-cyano-4-nitroaniline are dissolved in 400 parts by weight of concentrated sulphuric acid at O-15 C. and diazotized with parts by volume of nitrosyl sulphuric acid (42 g. of nitrite in 100 ml. of H 80 with good stirring and cooling, and poured into about 3000 parts by weight of ice after about 3 hours. A small excess of nitrite is removed with amidosulphonic acid and the solution is filtered. This solution is then combined with a solution of 29.7 parts by weight of the amino compound of the formula ll C H OCOCHa partly neutralised with dilute caustic soda and the coupling completed with sodium acetate. The dyestuff is filtered and washed. It forms in the dry state a black-red powder, which dissolves in organic solvent, such as acetone or alcohol, with a red colour. When finely dispersed by means of suitable additives, it dyes acetate rayon and synthetic super polyamide fabrics in clear red shades of good washing and light fastness.

In the same way, from the corresponding starting materials, the following dyestuifs can be produced, which dye fabrics of aromatic polyesters, such as polyethylene terephthalates, in the specified shades C11140 (6 0 CH;

Ruby.

Red-violet.

Orange.

Red-violet.

Violet.

Reddlsh orange.

Red.

Reddlsh orange.

Yellowish red.

Reddjsh yellow.

Yellowish orange.

Strongly yellowish orange.

Red.

Strongly yellowish orange:

Yellowish orange;

Reddish orange:

wherein X and Y have the above meaning and at least one of the radicals R and R' represent a hydroxyalkyl group can be used as starting materials in the above reaction for preparing the coupling components.

Example 2 16.3 parts by Weight of 2-cyano-4-nitroaniline are dissolved at 0-15" C. in 400 parts by weight of concentrated sulphuric acid and the amino compound then diazotized by means of 170 parts by volume of nitrosyl sulphuric acid (42 parts by weight of sodium nitrite in 100 m1. of

sulphuric acid) with good stirring and cooling; after a reaction time of 3 hours the mixture is poured onto about 3000 parts by weight of ice. A slight excess of nitrite is destroyed by means of amido-sulphonic acid and the solution then filtered. The solution of the diazonium compound thus prepared is combined with an aqueous solution of 34.4 parts by weight of the amino compound of the formula 1? G acomo o o CHa)! I IHOO0H it is then partially neutralized with dilute soda lye and the coupling completed while adding sodium acetate. The dyestuff obtained is filtered and washed. When dry it represents a black-red powder which dissolves in organic solvents, such as alcohol or acetone, with red-violet coloration. The dyestufl dyes fibres of aromatic polyesters, such as of polyethylene terephthalate in finely dispersed form clear red-violet shades having good fastness to Washing and to light.

In a similar manner the dyestufls listed in the following table are obtainable from the corresponding starting materials; they yield on polyethyleneterephthalates and on fibres of aromatic polyesters produced from terephthalic acid and 1,4-bis-hydroxymethyl-cyclohexane fast dyeings having the below-indicated shades.

Violet.

NHC O CH:

I I Cl-N=NN(CzH2O o o 011m Red.

I I C'N CH:

I N ON=NC N(C2H2O o 0 0 01392 Red.

I OzN-N=N N(C H4O o 0 0 011m Bluish red.

I ON 01 31 O2NN=NN 021140 c o 0 CH2) 2 Do.

I o N (3112 I O2NN=N DN(C2H4O o 0 o 0H2 2 Violet.

I CN NH0 0 0112 I I C 2H5 02N--N=N-N\ Reddisb blue.

| c2112 0 o o 0 0 H2 ON NH0 0 0 CH3 1I3r 01-12 o N-ON=N- -N(C2H2O o o 0 01-192 Navy-blue.

I N02 NHCONHa I N OC N=NC N 021120 c 0 0 0112) 2 Red.

I I NC 01 V CH3 0 O C- -N:N- -N\ Orange.

| onnocoocrn NH 0 0 0211,

Example 3 wherein K is a member selected from the class consist- 4 parts by weight of the first-mentioned dyestufi? in EX- ample 2 are finely dispersed with the aid of 4 parts by weight of an emulsifying =polyglycolether and made up to a dye-bath of 8 l. of water which additionally contains 16 parts by weight of a carrier, e.g. benzoic acid, and 20 parts by weight of diammonium phosphate; 250 parts by weight of polyethyleneterephthalate fibres are introduced into this dye-bath at C. and the temperature of the bath raised to the boil within 30 minutes. The dyeing is then continued at boiling temperature for further 1 /2 to 2 hours. The dyed fibres are subsequently washed alkaline at 70 C. for 20 minutes, rinsed and dried. A clear red-violet dyeing is thus obtained which exhibits good light and wet fastness properties and which is further distinguished by good thermofixing properties.

I claim:

1. A compound free of sulfonic and carboxylic acid groups and having the formula Y K I (M) n I Y is a member selected from the class consisting of hydrogen and lower alkoxy; R is -z-oc0R wherein Z is lower alkylene having 2-4 carbon atoms and R is a member selected from the group consisting of lower alkyl and cyano lower alkyl; R is a member .15 selected from the group consisting of lower alkyl, cyano lower alkyl and 2. An azo dyestuff free of sulfonic and carboxylic acid groups and having the formula OCH;

magmat c} CN CH3 4. The dyestutf of the formula 5. The dyestuff of the formula 6. The dyestuflf of the formula 7. The dyestuff of the formula 8. The dyestuif of the formula 01 WGM WMOCHW I O1 Q a 16 9. The dyestutf of the formula 10. The dyestuif of the formula OZN-OAEN-OMCQHiO 0000 113):

NHCOCHa 11. The dyestuff of the formula NHCOCHa 12. The dyestuff of the formula CN NHCOCHa 13. The dyestuif of the formula QM-Q ON NHCOCH:

14. The dyestuff of the formula References Cited by the Examiner UNITED STATES PATENTS 2,249,749 7/1941 Dickey et al. 260207.1 X 2,283,327 5/1942 Felix et al. 260-207.1 2,888,450 5/1959 Kruckenberg 260207.1 X 2,971,953 2/1961 Rhyner 260-207.1

FOREIGN PATENTS 856,348 12/1960 Great Britain.

CHARLES B. PARKER, Primary Examiner.

R. J. FINNEGAN, D. M. PAPUGA,

Assistant Examiners. 

1. A COMPOUND FREE OF SULFONIC AND CARBOXYLIC ACID GROUPS AND HAVING THE FORMULA FI-01 WHEREIN K'' IS A MEMBER SELECTED FROM THE CLASS CONSISTING OG CYANO, BROMO, CHLORO, NITRO, LOWER ALKYL, LOWER ALKOXY, CARBO LOWER ALKOXY, TRIFLUOROMETHYL, PHENYL, LOWER ALKYL SULFONYL, PHENYL SULFONYL, CARBONAMIDE AND LOWER ALKYL-SUBSTITUTED CARBINAMIDE; L IS A MEMBER SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, CYANO AND NITRO; M IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF CHLORO AND BROMO, N BEING AN INTEGER OF 0-3 WHEN M IS CHLORO, AND 0-1 WHEN M IS BROMO; X IS A MEMBER SELECTED FROM THE CLASS CONSISTING OF 